Structural, inorganic, and adsorptive properties of hydrochars obtained by hydrothermal carbonization of coffee waste.

The hydrothermal carbonization process is a suitable process for the conversion of potentially harmful lignocellulosic waste into hydrochars. Defective coffee beans were the precursor raw material for hydrochar synthesis. Reactions were performed in a high-pressure reactor at 150, 200, and 250 °C, in autogenous pressure, for 40 min. Hydrochars were recovered by filtration and characterized by energy dispersive X-ray fluorescence spectroscopy, UV-Vis spectrophotometry, attenuated total reflection Fourier-transform infrared spectroscopy, differential thermal analysis, and scanning electron microscopy. Methylene blue adsorption tests were performed and analyzed by Langmuir and Freundlich adsorption isotherms. Adsorption mechanisms were investigated by computational calculations at DFT level. Results suggest that hydrochars from defective coffee beans can be applied as technological resources in the agronomic and environmental fields due to their inorganic composition, mainly to high magnesium content, the structural characteristics of porosity, biodegradation control, soil carbon-fixation and adsorption capacity. Important adsorption processes are caused by the development of oxygenated functional groups on the hydrochar surface.

Iron and molybdenum mixed oxide supported on Al-PILC for the catalytic oxidative desulfurization of dibenzothiophene in simulated diesel fuel.

In this work, three novel catalysts were prepared by 2.5, 5.0, and 10.0 wt.% facile impregnation with an iron and molybdenum mixed oxide (Fe/Mo) on an aluminum pillared clay (Al-PILC) support. These materials were characterized by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), X-ray diffraction (XRD), temperature programed reduction (TPR), and nitrogen (N2) physisorption at 77 K. Characterizations indicated that the metal particles were dispersed on the surface of the three catalysts, and the interlayer d001 spacing of the pillared material remained unchanged after the impregnation process. The catalytic tests showed good results for DBT oxidation using the synthesized catalysts, with high turnover frequency (TOF) values, particularly for the material with 5.0 wt.% Fe/Mo. Theoretical calculations were carried out at the density functional theory (DFT) level, to investigate how the DBT molecules were adsorbed onto the surface of the mixed oxide. The lowest energy proposal was obtained when both Fe and Mo were present at the active sites, indicating a possible synergistic effect of the metals on catalyst activity. Reuse tests indicated that the catalysts could be employed effectively for up to 3 cycles in a row, then a decrease in activity occurred and the active sites needed to be regenerated.

Hydrochar production from defective coffee beans by hydrothermal carbonization.

This study aimed to produce and characterize hydrochars from defective coffee beans and its application as a solid fuel. Defective coffee beans were used as precursor residue for hydrochar synthesis. Reactions were run in a high-pressure reactor at temperatures of 150, 200 and 250 °C, under autogenesis pressure, for 40 min. Solid phase was recovered by filtration and characterized by CHNO-S analyzer, thermogravimetric analysis and differential scanning calorimetry. Hydrothermal carbonization temperature was key to change energy values and fuel properties. These results suggest hydrothermal carbonization is an effective and simple strategy for converting coffee waste into functional, high-quality, and energy-dense solid biofuels.

Rapid extraction of melamine in powdered milk for direct electrospray ionization tandem mass spectrometry analysis.

A combination of a simple pretreatment for melamine extraction and direct analysis in electrospray ionization tandem mass spectrometry (ESI-MS/MS) is proposed. Three pretreatments were evaluated. The first was based on suppressing interference using acetonitrile. The second used sulphuric acid and trichloroacetic acid to suppress interference and for melamine extraction, respectively. The third used sulphuric acid to suppress milk interference, trichloroacetic acid for melamine precipitation, and ethyl acetate for melamine extraction. However, only the last pretreatment suppressed milk interference in melamine detection and a good linearity (R(2)=0.99) was obtained. The presence of MS/MS 85 on melamine fragmentation spectrum showed the selectivity of this method. The limit of detection and limit of quantification were 0.269 µg L(-1) and 0.897 µg L(-1), respectively. The recoveries and relative standard deviation (RDS) of method were lower than 114% and 7.86%, respectively. Further, the research was extended to elucidate the nature of the melamine in the extract through infrared spectroscopy and microscopy analyses. The precipitate was characterized as melaminium bis(trichloroacetate) dihydrate, which is generated through hydrogen bound formation in an interaction between melamine and trichloroacetic acid. Therefore, a simple, fast, and easy method for melamine extraction and direct ESI-MS/MS analysis was developed.

Fenton-like processes and adsorption using iron oxide-pillared clay with magnetic properties for organic compound mitigation.

In this work, a new step was added to the classic route of iron-pillared clay obtention, resulting in a material with both magnetic and oxidative properties. The saturation of the material surface intercalated with trinuclear acetate-hydroxo iron (III) nitrate in glacial acetic acid atmosphere before heat treatment promoted magnetic phase formation (FePMAG). The material was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), nitrogen adsorption/desorption isotherms, scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS), and X-ray photoelectron spectroscopy (XPS). FePMAG showed an increase of 0.57 nm in basal spacing which contributed to the specific surface area increase from 39.1 to 139.2 m(2)/g. The iron phase identified by XRD and XPS was maghemite, with a little presence of hematite formed by the trinuclear acetate-hydroxo iron (III) nitrate decomposition during heat treatment. In the adsorption tests, FePMAG displayed a good capacity for organic dye methylene blue (MB) removal, reaching 41 % at 150 min. Under photo-Fenton conditions, the material showed an excellent MB oxidation capacity, completely removing the color of the solution within 90 min. Identification of the oxidation products with lower molecular (m/z = 160, 220, and 369) mass was performed by electrospray ionization mass spectroscopy (ESI-MS).

Activated carbon prepared from coffee pulp: potential adsorbent of organic contaminants in aqueous solution.

The processing of coffee beans generates large amounts of solid and liquid residues. The solid residues (pulp, husk and parchment) represent a serious environmental problem and do not have an adequate disposal mechanism. In this work, activated carbons (ACs) for adsorption of organic compounds were prepared from coffee pulp by controlled temperature at different pulp/Na2HPO4 ratios (4:1, 2:1, 5:4 and 1:1). The N2 adsorption/desorption isotherms showed ACs with high quantities of mesopores and micropores and specific surface areas of 140, 150, 450 and 440 m(2)g(-1) for AC 4:1, AC 2:1, AC 5:4 and AC 1:1, respectively. The prepared material AC 5:4 showed a higher removal capacity of the organic contaminants methylene blue (MB), direct red (DR) and phenol than did a Merck AC. The maximum capacities for this AC are approximately 150, 120 and 120 mg g(-1) for MB, DR and phenol, respectively. Thus, a good adsorbent was obtained from coffee pulp, an abundant Brazilian residue.

A friendly environmental material: iron oxide dispersed over activated carbon from coffee husk for organic pollutants removal.

A friendly environmental material for organic contaminants removal was prepared in this work: small particles of iron oxide dispersed over activated carbon from coffee waste for Fenton-like application. The materials were characterized by means of XRD, N2 physisorption, Mössbauer spectroscopy and H2 pulse titration. The composites showed very good catalytic performances for methylene blue organic dye oxidation. The small goethite particles are the predominant iron oxide phase in the composites. The apparent surface area is quite high and is not very affected after iron impregnation. ESI-MS studies revealed that the dye removal occurs through a Fenton-type system by the composite whereas for the activated carbon the dye removal occurs mainly via adsorption. The iron leaching from the catalysts was negligible, less than 0.5 ppm, which evidences the occurrence of a heterogenous oxidation process. The catalyst was very active for methylene blue oxidation and could be repeatedly used for at least 5 cycles. The catalyst was also active in the oxidation of other organic compounds, such as caffeine and atrazine.

Caracterização físico-química da mucilagem de inhame liofilizada / Physical and chemical characteristics of the mucilage of lyophilized yam

A mucilagem do inhame desempenha papel de interesse na indústria de alimentos em razão das suas propriedades como espessante, estabilizante e emulsificante. Neste estudo, objetivou-se caracterizar a mucilagem liofilizada do inhame por meio de análises físicas, químicas e reológicas. Foram determinados a composição centesimal, valor calórico, pH, acidez, sais minerais, vitamina C, açúcares totais, polifenóis, pectinametilesterase, poligalacturonase, termogravimétrica, análise térmica diferencial, calorimetria diferencial de varredura, espectroscopia infravermelho e viscosidade aparente. A mucilagem de inhame liofilizada apresentou elevados teores de proteína bruta e fibra alimentar e baixos teores de fração glicídica e de valor calórico. Quanto à análise termogravimétrica a mucilagem de inhame demonstrou maior perda de massa cerca de 60 por cento à temperatura média de 200º C, o que inviabiliza o seu uso acima desta temperatura.

The mucilage of yam is of interest in the food industry due to its properties as a thickener, stabilizer and emulsifier. The aim of this study was to characterize the freeze-dried mucilage of yam through physical analysis, chemical and rheological properties. The study measured the proximate composition, caloric value, pH, acidity, minerals, vitamin C, sugars, polyphenols, pectin methylesterase, polygalacturonase, thermogravimetric, differential thermal analysis, differential scanning calorimetry, infrared spectroscopy and viscosity. The lyophilized yam mucilage showed high levels of crude protein and dietary fiber content and low fraction of glucose and calories. A thermogravimetric analysis mucilage of the yam showed a higher weight loss (about 60 percent) at an average temperature of 200º C, thus precluding their use above this temperature.

Efeito de frações tânicas sobre parâmetros biológicos e nutricionais de Spodoptera frugiperda (Lepidoptera: Noctuidae) / Effect of tanical fractions on biological and nutritional parameters of Spodoptera frugiperda (Lepidoptera: Noctuidae)

Conduziu-se este trabalho, com o objetivo de quantificar taninos condensados presentes nas cascas do caule de Ochroma pyramidalis (Bombacaceae), Schinus terebinthifolius (Anacardiaceae), Enterolobium contortisiliquum (Fabaceae) e Peltophorum dubium (Fabaceae) e verificar o efeito de frações tânicas dessas espécies sobre parâmetros biológicos e nutricionais de S. frugiperda. A partir das cascas das espécies vegetais se prepararam extratos, dos quais alíquotas foram tomadas para a quantificação dos taninos. Em seguida, os extratos foram submetidos a fracionamento para a obtenção das frações tânicas, que foram incorporadas à dieta artificial e oferecidas para lagartas de S. frugiperda. Todas as espécies vegetais estudadas apresentaram taninos condensados, sendo que S. terebinthifolius apresentou menor quantidade desses compostos. A fração tânica de P. dubium causou redução no peso das lagartas e pupas, diminuição na sobrevivência de S. frugiperda durante as fases larval e pupal, e acarretou menor consumo alimentar, além de prolongar a duração das fases imaturas desse inseto. O tratamento com S. terebinthifolius causou redução na percentagem de sobrevivência, durante a fase de pupa. Pupas provenientes de lagartas que receberam tratamento com a fração de E. contortisiliquum tiveram aumento no seu período de desenvolvimento. Lagartas alimentadas com a fração proveniente de P. dubium apresentaram a menor taxa de crescimento relativo (RGR), menor eficiência de conversão do alimento digerido (ECD) e maior custo metabólico (CM). A digestibilidade aproximada (AD) foi maior para os tratamentos com as frações tânicas de P. dubium e S. terebinthifolius.

The objective of this study was to quantify condensed tannins present in the stem bark of Ochroma pyramidalis (Bombacaceae), Schinus terebinthifolius (Anacardiaceae), Enterolobium contortisiliquum (Fabaceae) and Peltophorum dubium (Fabaceae) and to verify the effect of tannic fractions of these species on biological and nutritional parameters of S. frugiperda. Extracts were prepared from the barks of the plant species and aliquots were taken from them to quantify the tannins. The extracts were then submitted to fractionation to obtain the tannic fractions, which ones were incorporated into an artificial diet and offered to the larvae of S. frugiperda. All the studied species showed condensed tannins, and S. terebinthifolius showed the lowest amount of these compounds. The tannin fraction of P. dubium caused a reduction in the weight of larvae and pupae, decreased the survival of S. frugiperda during the larval and pupal stages and led to a reduction of intake, beyond to extend the duration of immature stages of this insect. The treatment with S. terebinthifolius caused a reduction in the survival percentage during the pupal stage. Pupae from larvae that received the treatment with the fraction of E. contortisiliquum had an increase in its development period stage. Larvae fed with the fraction from P. dubium showed the lowest relative growth rate (RGR), lower efficiency of conversion of ingested food (ECI) and a higher metabolic cost (CM). The approximate digestibility (AD) was higher for the treatments with tannic fractions of P. dubium and S. terebinthifolius.

Influência da polaridade de pesticidas não-iônicos sobre sua sorção em um latossolo / Influence of the polarity of non-ionic pesticides on their sorption by a latosoil

Investigou-se a influência da polaridade de pesticidas não-iônicos sobre sua sorção em material do horizonte A de um Latossolo Vermelho Acriférrico típico. Foram estudados treze pesticidas, abrangendo uma ampla faixa de polaridade, expressa na forma do coeficiente de partição do composto entre n-octanol e água (Kow). Foram obtidas as isotermas de sorção dos pesticidas, agitando-se subamostras do solo com soluções aquosas dos mesmos, sendo suas determinações quantitativas feitas por cromatografia líquida de alta eficiência. As isotermas de sorção dos pesticidas revelaram-se bem ajustadas ao modelo de Freundlich, com seus valores de coeficiente de sorção (Kf) variando de 0,2 a 202 mL.nmol-1. Os valores de log Kf e de log Kow dos pesticidas mostraram-se linearmente correlacionados (R² = 0,87), indicando que a partição hidrofóbica na matéria orgânica foi o principal mecanismo de sorção dos compostos no solo. Para a maioria dos pesticidas, os valores de Kf obtidos foram maiores do que aqueles previstos pela equação de Briggs (1981), a qual relaciona o valor de Kf do pesticida com o seu valor de Kow e o teor de matéria orgânica do solo. Assim, os resultados mostraram que a referida equação, obtida em solos da Inglaterra, não é adequada para a previsão do valor de Kf de pesticidas no solo estudado, e que a natureza da matéria orgânica pode ser um importante fator a influenciar a sorção de pesticidas não-iônicos em solos.

The sorption of thirteen non-ionic pesticides, with varying n-octanol/water partition coefficients (Kow), by soil material taken from the A horizon of an Acriferric Red Latosol was investigated. Sorption isotherms of the pesticides were determined by the shake flask method. The concentrations of the chemicals in aqueous solutions were measured by HPLC with UV detector. Sorption isotherms of all compounds fitted well the Freundlich model, with sorption coefficient (Kf) values ranging from 0,2 to 202 mL.nmol-1. Log Kf values were shown to be linearly correlated (R² = 0,87) with the log Kow values of the pesticides, revealing that hydrophobic partitioning onto organic matter was the dominant mechanism of their sorption by the studied soil. For most compounds, the observed Kf values were higher than those predicted by the Briggs (1981) equation, which relates the Kf of the pesticide to its Kow and to the content of organic matter in the soil. These results showed that this equation, which was obtained for soils from England, is not adequate do predict the Kf values of pesticides for the soil studied in this work, and that qualitative aspects of soil organic matter may be an important factor to affect the sorption of non-ionic pesticides by soils.

Lixiviação do inseticida thiamethoxam em macrolisímetros de duas classes de solo / Leaching of the insecticide thiamethoxam in macrolysimeters of two soil classes

Investigou-se a lixiviação do inseticida thiamethoxam em dois solos da região de Lavras-MG, pertencentes às classes Latossolo Vermelho Acriférrico típico (LVwf) e Argissolo Vermelho-Amarelo Distrófico típico (PVAd). Foram utilizados macrolisímetros desses solos, com 1,0 m de diâmetro e 0,45, 0,90 e 1,80 m de profundidade, os quais foram obtidos mantendo-se a estrutura original dos solos. A aplicação do inseticida foi feita no início do período chuvoso, utilizando-se o produto comercial Actara 250 WG, o qual foi diluído em 100 mL de água e aplicado na superfície dos lisímetros. Os lisímetros foram mantidos sem vegetação e sob regime hídrico natural. A água percolada nos mesmos, até o final do segundo período chuvoso após a aplicação, foi coletada e analisada com relação à concentração de thiamethoxam, cuja determinação foi feita por CLAE. Os resultados mostraram alta mobilidade do thiamethoxam em ambos os solos, sendo que sua lixiviação foi mais intensa no PVAd do que no LVwf. As porcentagens totais de thiamethoxam lixiviadas abaixo de 0,45 m foram, em média, equivalentes a 53,8 e 19,4% da quantidade aplicada, respectivamente para o PVAd e LVwf. Resíduos de thiamethoxam foram detectados também na água percolada nos lisímetros de 0,90 e 1,80 m de ambos os solos. Embora o estudo tenha sido conduzido em solos sem vegetação, os resultados obtidos indicaram elevado potencial de lixiviação do thiamethoxam nos solos estudados, em condições práticas de uso desse inseticida.

The leaching of thiamethoxam in two Brazilian soils, a typic Acriferric Red Latosol (LVwf) and a typic Dystrophic Red-Yellow Argisol (PVAd), was investigated in macrolysimeters (1.0 m diameter and depth of 0.45, 0.90 and 1.80 m) of undisturbed material of the soils, which were kept without vegetation and under field conditions. The insecticide was applied at the beginning of the rainy season, using the formulation Actara 250 W®, which was diluted in 100 mL of water and applied on the lysimeters surface. The water percolated through the lysimeters was collected until the end of rainy season of the following year, with samples being taken for determination of thiamethoxam concentration, performed by HPLC. The results showed a high mobility of thiamethoxam in both soils, with more intense leaching of the compound in the PVAd than in the LVwf. The total amounts of thiamethoxam leached below 0.45 m were equivalent to 53.8 and 19.4% of the applied amount, respectively for the PVAd and LVwf. Thiamethoxam residues were also found in the water collected from the 0.90 and 1.80 m lysimeters of both soils. These results indicate a high potential of thiamethoxam leaching under practical conditions of its use in the studied soils, despite the lack of vegetation.

Produção de carvão a partir de resíduo de erva-mate para a remoção de contaminantes orgânicos de meio aquoso / Production of charcoal from maté waste to remove organic contaminants from aqueous solution

Neste trabalho, apresenta-se um novo material adsorvente, obtido a partir da pirólise de resíduos da erva-mate. O carvão resultante demonstrou elevada área superficial específica quando comparado com outros materiais pirolisados e elevada capacidade de remoção de contaminantes orgânicos de soluções aquosas. Os valores de área específica apresentados pelos materiais foram de 344, 191 e ~0,5 m² g-1, para o carvão Mate 1, Mate 2 e Mate 3, respectivamente. As isotermas de adsorção mostraram que os carvões apresentam potencial para utilização como adsorvente para compostos orgânicos, tais como: o corante têxtil vermelho reativo, o corante azul de metileno e para o herbicida atrazina, sendo que os máximos de adsorção utilizando o carvão Mate 1 foram de 16, 230 e 30 mg g-1, respectivamente.

In this work we present a new adsorbent material, obtained by maté waste pyrolisis. The resulting charcoal presented high specific area when compared with other pyrolized materials and also high capacity to remove organic contaminants from aqueous solution. The charcoal showed specific area of 344, 191 and ~0.3 m² g-1 for sample Mate 1, Mate 2 and Mate 3, respectively. According to the corresponding adsorption isotherm these materials present good adsorption capacity for reactive textile and methylene blue dyes and the herbicide atrazine. Adsorption maxima were respectively 16, 230 and 35 mg g-1 for such substances, when sample Mate 1 was used.

Frações de fosfato em resrvatíorios de água em Lavras - MG / Fractions of phosphate in water bodies in Lavras - MG

O presente estudo teve como objetivo determinar os teores e as frações de P presentes nos corpos d'água de reservatórios no Campus da Universidade Federal de Lavras, verificando a eventual presença de condições de eutrofização. Foram selecionados oito reservatórios dentro do Campus, representando as condições de uso e manejo do solo. As amostragens foram realizadas mensalmente, com início em janeiro e término em dezembro de 2004. Foram quantificados os níveis de P, nas seguintes formas: ortofosfato solúvel (OPS), ortofosfato total (OPT), P solúvel total (PST), P total (PT), P particulado total (PPT), P não reativo solúvel (PNRS), P não reativo particulado (PNRP) e o ortofosfato particulado (OPP). Foram também avaliados os parâmetros: pH, condutividade eletrolítica, Ca, Mg, Na, K, NO-3, NO-2 e NH+4 . Os limites de detecção do método e os limites de quantificação foram determinados. Os valores encontrados de OPS para os corpos d água sempre estiveram abaixo do permitido pela Resolução CONAMA 357/05. No entanto, outras frações de P apresentaram teores elevados, refletindo as precipitações pluviométricas e as condições do solo. Esses teores mais elevados têm caráter momentâneo e, no geral, estes corpos d'água podem ser considerados de excelente qualidade quanto à presença de P. O manejo do solo dentro do Campus da UFLA e o tratamento aplicado a efluentes e águas residuárias de granjas e estábulos mostraram, no geral, serem adequados, não oferecendo grandes riscos de eutrofização aos cursos d'água que cortam o campus.

The objective of this study was to evaluate the contents and fractions of P in water bodies at the Campus of the Federal University of Lavras to verify the occurrence of eutrophication. Eight artificial lakes were chosen, representing the conditions of soil use and management in the campus. The samples were collected monthly from January to December 2004. The levels of P in the following forms were assessed: soluble orthophosphate (OPS), total orthophosphate (OPT), total soluble P (PST), total P (PT), total particulate P (PPT), soluble non-reactive P (PNRS), non-reactive particulate P (PNRP), and total particulate orthophosphate (OPP). The pH, electrolytic conductivity, Ca, Mg, Na, K, NO-3, NH+4 and NO-2 were also evaluated. The contents of OPS were below those allowed by the CONAMA 357/05 Resolution. Nevertheless, other fractions of P were present in high contents, reflecting the soil conditions and the rainfall. Episodes of high P contents were momentary. In general, these water bodies may be considered of excellent quality concerning the P contents. Soil management in the Campus and the treatment applied to effluents and waste waters appear to be suitable avoiding eutrophication.